Polyether polyol and polyurethane compositions protected against oxidation and core scorching

ABSTRACT

Described are compositions protected against thermal and oxidative degradation that comprise 
     A) a polyether polyol or mixtures of such polyols, 
     B) at least one benzofuranone derivative of formula I, ##STR1##  wherein L, G, m, R 1  to R 5  and R 21  to R 24  are as defined in claim 1, 
     C) at least one compound from the group of the phenolic anti-oxidants, and/or 
     D) at least one compound from the group of the amino anti-oxidants of the secondary amine type. Also polyurethane(s) (foam(s)) prepared therefrom are protected against thermal and oxidative degradation, especially against core scorching.

The invention relates to polyether polyol and polyurethane compositionsthat are protected especially against oxidation and against theundesired phenomenon of core scorching during the preparation ofpolyurethane foam by the presence of at least one benzofuran-2-onederivative and at least one further compound from the group of thephenolic anti-oxidants and/or from the group of the amino anti-oxidantsof the secondary amine type, as well as to the use of the saidderivatives and compounds as additives for the prevention of the saidphenomena, and to a process for the preparation of polyurethane usingthose derivatives and compounds.

Currently, 2,6-di-tert-butyl-4-methylphenol ("butylated hydroxytoluene","BHT") is generally used in practice for the above-mentioned purposes,but the improvements in stabilisation achieved with it are notsatisfactory.

Combinations of specific anti-oxidants have also been proposed, such asmixtures of sterically hindered phenols (see, for example, U.S. Pat. No.3,280,049, U.S. Pat. Nos. 4,007,230, 3,494,880), or mixtures ofsterically hindered phenols with specific diphenylamines (see, forexample, U.S. Pat. Nos. 4,070,304, 4,265,783, 4,275,173 and 4,021,385).The stabilisers and/or mixtures of stabilisers proposed in thosespecifications do not, however, meet the stringent demands made on themin practice.

Benzofuranone derivatives are already known as stabilisers for variousorganic materials (e.g. U.S. Pat. No. 4,611,016; EP-0 415 887).

Surprisingly, it has now been discovered that it is possible to preparecompositions that are very effectively protected against oxidation byadding to polyether polyols a combination of at least onebenzofuran-2-one derivative with at least one further anti-oxidant fromthe group of the phenolic anti-oxidants and/or the amino anti-oxidantsof the secondary amine type, from which compositions it is possible toproduce polyurethane foams without the interference of core scorching.

The invention thus relates to compositions comprising

A) a polyether polyol or mixtures of such polyols,

B) at least one benzofuranone derivative of formula I ##STR2## wherein Lis oxygen or, when G is a direct bond and R₁ is hydrogen, C₁ -C₄ alkylor C₁ -C₄ alkoxy, does not exist,

G is a direct bond or a group --CR₁₈ R₁₉ --CO--,

m is 1 or 2,

R₁, when m=1 and G is a direct bond, is hydrogen, C₁ -C₂₅ alkyl, C₃ -C₂₅alkenyl, C₂ -C₁₈ alkanoyl, C₃ -C₂₅ alkenoyl, C₇ -C₉ phenylalkyl,unsubstituted or C₁ -C₄ alkyl-substituted phenyl, unsubstituted or C₁-C₄ alkyl-substituted C₅ -C₈ cycloalkyl, C₃ -C₂₅ -alkyl, -alkanoyl or-alkenyl interrupted by oxygen, sulfur or by >NR₁₆, C₆ -C₉cycloalkoxycarbonyl, benzoyl or C₁ -C₁₂ alkyl-substituted benzoyl,

or

R₁, when m=2 and G is a direct bond, is --CO--R₁₇ --CO--,

or

R₁, when m=1 and G is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₃₀alkoxy, C₃ -C₃₀ alkoxy interrupted by oxygen, sulfur or by >NR₁₃, C₇ -C₉phenylalkoxy, C₅ -C₁₂ cycloalkoxy, cycloalkoxy, C₂ -C₁₈ alkenyloxy,unsubstituted or C₁ -C₁₂ alkyl-substituted phenoxy, ##STR3## or R₁, whenm=2 and G is a group --CR₁₈ R₁₉ --CO--, is C₂ -C₁₂ alkanedioxy, C₃ -C₂₅alkanedioxy interrupted by oxygen, sulfur or by >NR₁₆, ##STR4## R₂ andR₄ are each, independently of the other, hydrogen or C₁ -C₆ alkyl,

R₃ and R₅ are each, independently of the other, hydrogen, C₁ -C₂₅ alkyl,C₇ -C₉ phenylalkyl, unsubstituted or C₁ -C₄ alkyl-substituted phenyl,unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈ cycloalkyl, C₁ -C₁₈alkoxy, hydroxy, C₁ -C₂₅ alkanoyloxy, C₃ -C₂₅ alkenoyloxy, C₃ -C₂₅alkenyloxy interrupted by oxygen, sulfur or by >NR₁₆, C₆ -C₉cycloalkylcarbonyloxy, benzoyloxy or C₁ -C₁₂ alkyl-substitutedbenzoyloxy, or a radical of the formula --(CH₂)_(n) --CO--OR₆,--(CH₂)_(n) --COR₁₁, or --(CH₂)_(n) --CO--N(R₇)₂,

R₃, when m=1, is furthermore a radical of the formula --(CH₂)_(n)--CO--O--A*--O--CO--(CH₂)_(n) --E, --(CH₂)_(n) --CO--NR₈ --A*--NR₈--CO--(CH₂)_(n) --E, --(CH₂)_(n) --CO--NR₈ --A*--O--CO--(CH₂)_(n) --E,##STR5## or when m=1 and R₄, R₅, R₂₁ and R₂₄ are hydrogen, R₃ inaddition is a radical of the formula ##STR6## R₂ together with R₃ or R₄together with R₅, in each case together with the carbon atoms to whichthey are bonded, form a phenyl ring,

R₆ is hydrogen, C₂ -C₁₈ alkyl, C₁ -C₁₈ alkyl interrupted by oxygen orsulfur, C₃ -C₁₆ dialkylaminoalkyl, cyclohexyl, phenyl, or phenylsubstituted by from 1 to 3 alkyl radicals together having a maximum of18 carbon atoms,

n is 0, 1 or 2, the substituents

R₇ are each, independently of the other, hydrogen, C₁ -C₁₈ alkyl,cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkylradicals together having a maximum of 16 carbon atoms, a radical of theformula --C₂ H₄ OH, --C₂ H₄ --O--C_(q) H_(2q+1) or --C₂ H₄ --O--CO--R₁₀,or, together with the nitrogen atom to which they are bonded, form apiperidine or morpholine radical, wherein q is 1 to 18,

R₈ is hydrogen, alkyl having from 1 to 18 carbon atoms, cyclopentyl,cyclohexyl, phenyl, benzyl, phenyl substituted by 1 or 2 alkyl radicalstogether having a maximum of 16 carbon atoms,

R₉ is alkyl having from 1 to 18 carbon atoms,

R₁₀ is hydrogen, alkyl having from 1 to 22 carbon atoms or cycloalkylhaving from 5 to 12 carbon atoms,

R₁₁ is hydroxy, ##EQU1## C₁ -C₁₈ alkoxy or --NR₁₄ R₁₅, R₁₂ and R₁₃ areeach, independently of the other, hydrogen, C₁ -C₁₂ alkyl or phenyl, orform together with the C-atom to which they are bound a C₅ -C₇-alkylidene-ring which is unsubstituted or substituted by 1 to 3 C₁ -C₄alkyl groups,

R₁₄ and R₁₅ are each, independently of the other, hydrogen or C₁ -C₁₈alkyl, M is an r-valent metal cation and r is 1, 2 or 3,

A* is an alkylene radical having from 2 to 22 carbon atoms that may ormay not be interrupted by nitrogen, oxygen or by sulfur,

Y is --O--, --S--, --SO--, --SO₂ -- or --C(R₂₀)₂ --, wherein thesubstituents

R₂₀ are each, independently of the other, hydrogen, C₁ -C₁₆ alkyl,phenyl or a radical of the formula --(CH₂)_(n) --CO--OR₆ or --(CH₂)_(n)--CO--N(R₇)₂,

E is a radical of the formula ##STR7## R₁₆ is hydrogen or C₁ -C₈ alkyl,R₁₇ is a direct bond, C₁ -C₁₈ alkylene, C₂ -C₁₈ alkylene interrupted byoxygen, sulfur or by >NR₁₆, C₂ -C₁₈ alkenylene, C₂ -C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene, C₅ -C₈ cycloalkylene, C₇ -C₈ bicycloalkylene orphenylene,

R₁₈ and R₁₉ are each, independently of the other, hydrogen, C₁ -C₄ alkylor phenyl, and

R₂₁, R₂₂, R₂₃ and R₂₄ are each, independently of the others, hydrogen,C₁ -C₄ alkyl or C₁ -C₄ alkoxy, provided that at least one of theradicals R₂₁, R₂₂, R₂₃ and R₂₄ is hydrogen,

C) at least one compound from the group of the phenolic anti-oxidants,and/or

D) at least one compound from the group of the amino anti-oxidants ofthe secondary amine type.

In a further embodiment the invention relates to compositions comprising

A) a polyether polyol or mixtures of such polyols,

B) at least one benzofuranone derivative of formula Ia ##STR8## whereinR.sup.•₁ is phenyl, or phenyl substituted by from 1 to 3 alkyl radicalstogether having a maximum of 12 carbon atoms or by alkoxy having from 1to 12 carbon atoms,

R.sup.•₂ is hydrogen and R.sup.•₄ is hydrogen, alkyl having from 1 to 12carbon atoms, cyclopentyl, cyclohexyl or chlorine,

R.sup.•₃ has the same meaning as R.sup.•₂ or R.sup.•₄ or is a radical ofthe formula --(CH₂)_(n) --CO--OR.sup.•₆, --(CH₂)_(n) --CO--N(R.sup.•₇)₂,--(CH₂)_(n) --CO--O--A*--O--CO--(CH₂)_(n) --E.sup.•, --(CH₂)_(n)--CO--NR.sup.•₈ --A.sup.• --NR.sup..sup.•₈ --CO--(CH₂)_(n) --E.sup.•,--(CH₂)_(n) --CO--NR.sup.•₈ --A.sup.• --O--CO--(CH₂)_(n) --E.sup.•,##STR9## or --Y.sup.• --E.sup.• wherein R.sup.•₆ is hydrogen, alkylhaving from 2 to 18 carbon atoms, alkyl having from 1 to 18 carbon atomsthat is interrupted by oxygen or by sulfur, dialkylaminoalkyl having atotal of from 3 to 16 carbon atoms, cyclopentyl, cyclohexy, phenyl, orphenyl substituted by from 1 to 3 alkyl radicals together having amaximum of 18 carbon atoms,

n is 0, 1 or 2,

the substituents R.sup.•₇ are each, independently of the other,hydrogen, alkyl having from 1 to 18 carbon atoms, cyclopentyl,cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals togetherhaving a maximum of 16 carbon atoms, a radical of the formula --C₂ H₄OH, --C₂ H₄ --O--C_(q) H_(2q+1) or --C₂ H₄ --O--CO--R.sup.•₁₀, or,together with the nitrogen atom to which they are bonded, form apiperidine or morpholine radical,

q is from 1 to 18,

R.sup.•₁₀ is hydrogen, alkyl having from 1 to 22 carbon atoms orcycloalkyl having from 5 to 12 carbon atoms,

A.sup.• is an alkylene radical having from 2 to 22 atoms that may or maynot be interrupted by nitrogen, oxygen or by sulfur,

R.sup.•₈ is hydrogen, alkyl having from 1 to 18 carbon atoms,cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkylradicals together having a maximum of 16 carbon atoms, or benzyl,

R.sup.•₉ is alkyl having from 1 to 18 carbon atoms,

Y.sup.• is --O--, --S--, --SO--, --SO₂ -- or C(R.sup.•₁₁)₂ --,

the substituents R.sup.•₁₁ are each, independently of the other,hydrogen, alkyl wherein the alkyl radicals together have a maximum of 16carbon atoms, phenyl or a radical of the formula --(CH₂)_(n)--CO--OR.sup.•₆ or --(CH₂)_(n) --CO--N(R.sup.•₇)₂ wherein n, R.sup.•₆and R.sup.•₇ have the meanings given,

E.sup.• is a radical of the formula ##STR10## wherein R.sup.•₁, R.sup.•₂and R.sup.•₄ have the meanings given, and

R.sup.•₅ is hydrogen, alkyl having from 1 to 20 carbon atoms,cyclopentyl, cyclohexyl, chlorine or a radical of the formula--(CH₂)_(n) --CO--OR.sup.•₆ or --(CH₂)_(n) --CO--N(R.sup.•₇)₂ whereinR.sup.•₆ and R.sup.•₇ have the meanings given, or R.sup.•₅ together withR.sup.•₄ forms a tetramethylene radical,

C) at least one compound from the group of the phenolic anti-oxidants,and/or

D) at least one compound from the group of the amino anti-oxidants ofthe secondary amine type.

Preferably, the phenolic component C) corresponds to formula II,##STR11## wherein A is hydrogen, C₁ -C₂₄ alkyl, C₅ -C₁₂ cycloalkyl,phenyl-C₁ -C₄ alkyl, phenyl or a group --CH₂ --S--R₂₅ or ##STR12## D isC₁ -C₂₄ alkyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁ -C₄ alkyl, phenyl or agroup --CH₂ --S--R₂₅,

X is hydrogen, C₁ -C₁₈ alkyl or one of the groups --C_(a) H_(2a) --S_(q)--R₂₆, --C_(b) H_(2b) --CO--OR₂₇, --C_(b) H_(2b) --CO--N(R₂₉)(R₃₀),--CH₂ N(R₃₄)(R₃₅), ##STR13## R is hydrogen or a group of the formula--CO--CH═CH₂, G* is hydrogen or C₁ -C₁₂ alkyl,

R₂₅ is C₁ -C₁₈ alkyl, phenyl or a group --(CH₂)_(c) --CO--OR₂₈ or --CH₂CH₂ OR₃₃,

R₂₆ is hydrogen, C₁ -C₁₈ alkyl, phenyl, benzyl or a group ##STR14## R₂₇is C₁ -C₃₀ alkyl or one of the groups --CHR₃₁ --CH₂ --S--R₃₂, ##STR15##wherein Q is C₂ -C₈ alkylene, C₄ -C₆ thiaalkylene or a group --CH₂ CH₂(OCH₂ CH₂)_(d) --,

R₂₈ is C₁ -C₂₄ alkyl,

R₂₉ is hydrogen, C₁ -C₁₈ alkyl or cyclohexyl,

R₃₀ is C₁ -C₁₈ alkyl, cyclohexyl, phenyl, phenyl substituted by C₁ -C₁₈alkyl, or one of the groups ##STR16## R₂₉ and R₃₀ together are C₄ -C₈alkylene that may be interrupted by --O-- or --NH--,

R₃₁ is hydrogen, C₁ -C₄ alkyl or phenyl,

R₃₂ is C₁ -C₁₈ alkyl,

R₃₃ is hydrogen, C₁ -C₂₄ alkyl, phenyl, C₂ -C₁₈ alkanoyl or benzoyl,

R₃₄ is C₁ -C₁₈ alkyl, cyclohexyl, phenyl, phenyl substituted by C₁ -C₁₈alkyl, or a group ##STR17## R₃₅ is hydrogen, C₁ -C₁₈ alkyl, cyclohexyl,or a group ##STR18## or R₃₄ and R₃₅ together are C₄ -C₈ alkylene, whichmay be interrupted by --O-- or --NH--,

R₃₆ and R₃₇ are --S--C₁ -C₁₈ alkyl,

a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, c is 1 or 2, d is from 1 to 5, fis from 2 to 8 and q is 1, 2, 3 or 4.

Component C) corresponds more preferably to compounds of formula IIwherein

A is hydrogen, C₁ -C₈ alkyl, cyclohexyl, phenyl or a group --CH₂ --R₃₆or ##STR19## D is C₁ -C₈ alkyl, cyclohexyl, phenyl or a group --CH₂--R₃₇,

X is hydrogen, C₁ -C₈ alkyl or one of the groups --C_(a) H_(2a) --S_(q)--R₂₆, --C_(b) H_(2b) --CO--OR₂₇, --CH₂ N(R₃₄)(R₃₅), ##STR20## R₂₆ is C₁-C₁₂ alkyl, phenyl or a group --(CH₂)_(c) --CO--OR₂₈,

R₂₇ is C₁ -C₁₈ alkyl or a group ##STR21## wherein Q is C₂ -C₈ alkylene,--CH₂ --CH₂ --S--CH₂ CH₂ or a group --CH₂ CH₂ (OCH₂ CH₂)_(d) --,

R₂₈ is C₁ -C₁₈ alkyl,

R₃₄ and R₃₅ are each, independently of the other, hydrogen or C₁ -C₁₂alkyl or

R₃₄ and R₃₅ together are C₄ -C₈ alkylene which may be interrupted by--O-- or --NH--,

a is 1 or 2, b is 1 or 2, c is 1 or 2, and d is 1, 2 or 3.

Most especially preferred as component C) are compounds of formula IIwherein

A is hydrogen, C₁ -C₆ alkyl, --CH₂ --R₃₆ or a group ##STR22## D ishydrogen or C₁ -C₁₈ alkyl, and X is hydrogen, C₁ -C₄ alkyl, --CH₂ --R₃₆or a group of the formula ##STR23##

The amino component D) preferably corresponds to formula III ##STR24##wherein R₃₈ is C₁ -C₁₈ alkyl, phenyl--C₁ -C₄ alkyl, C₅ -C₁₂ cycloalkyl,phenyl, or phenyl or naphthyl substituted by C₁ -C₁₂ alkyl or by C₁ -C₁₂alkoxy,

R₃₉ is phenyl, naphthyl, or phenyl or naphthyl substituted by C₁ -C₁₂alkyl or by C₁ -C₁₂ alkoxy, or

R₃₈ and R₃₉ together form a radical of the formula IV ##STR25## whereinR₄₀ and R₄₁ are hydrogen or C₁ -C₁₈ alkyl or

R₄₁ is hydrogen or C₁ -C₁₈ alkyl and

R₄₀ together with R₄₂ forms a group of the formula ##STR26##

More preferably component D) corresponds to formula III wherein

R₃₈ und R₃₉ are each, independently of the other, phenyl or phenylsubstituted by C₁ -C₁₂ alkyl, or together form a radical of the formulaIV.

In formula III R₃₈ and R₃₉ most preferably form a radical of the formulaIV wherein R₄₀ and R₄₁ are C₆ -C₁₂ alkyl and R₄₂ is hydrogen, orcomponent D) is a commercial mixture obtained by reacting diphenylaminewith diisobutylene, comprising

a) diphenylamine;

b) 4-tert-butyldiphenylamine;

c) compounds from the group

i) 4-tert-octyldiphenylamine,

ii) 4,4'-di-tert-butyldiphenylamine,

iii) 2,4,4'-tris-tert-butyldiphenylamine,

d) compounds from the group

i) 4-tert-butyl-4'-tert-octyldiphenylamine,

ii) o,o'-,m,m'-, or p,p'-di-tert-octyldiphenylamine,

iii) 2,4-di-tert-butyl-4'-tert-octyldiphenylamine,

e) compounds from the group

i) 4,4'-di-tert-octyldiphenylamine,

ii) 2,4,-di-tert-octyl-4'-tert-butyldiphenylamine,

and wherein not more than 5% of component a), 8 to 15% b), 24 to 32% c),23 to 34% d) and 21 to 34% e) are present.

Alkyl substituents in the compounds of formulae I, II and III maycontain up to 30 carbon atoms. Examples of such substituents are methyl,ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl,dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl or docosyl andcorresponding branched isomers, especially tert-butyl, i-octyl andi-dodecyl. Alkoxy, alkanedioxy, alkanoyl and alkoxycarbonyl radicals areclearly derived from those groups as are also alkylene radicalscontained in the definitions of the substituents shown in formulaeI-III. The alkyl radicals listed and groups derived therefrom may beinterrupted by oxygen or by sulfur in order especially to formstructural units such as --CH₂ CH₂ --O--CH₂ CH₂ --, --CH₂ CH₂ --S--CH₂CH₂ -- or --O--(CH₂)₆ --O--.

Alkenyl radicals are derived from alkyl radicals by the replacement ofone or more C--C single bonds by C═C double bonds. Allyl and isoallylare preferred. Alkenyloxy is derived from alkenyl by adding --O--.

If some radicals are C₅ -C₁₂ cycloalkyl, then those include, forexample, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyland cyclododecyl. Cyclopentyl, cyclohexyl and cycloheptyl are preferred,with cyclohexyl being especially preferred. Cycloalkoxy andcycloalkoxycarbonyl radicals are derived therefrom by adding --CO-- or--O--CO-- groups.

Phenyl-C₁₋₄ alkyl and C₇ -C₉ phenylalkyl are, e.g., benzyl, phenethyl,3-phenylpropyl, α-methylbenzyl and α,α-dimethylbenzyl. Benzyl ispreferred.

The benzofuranones of formula I preferably used are those wherein

R₁, when m=1 and G is a direct bond, is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₈alkenyl, C₂ -C₁₈ alkanoyl, C₃ -C₁₈ alkenoyl, benzyl, phenyl or C₁ -C₄alkyl-substituted phenyl, C₅ -C₈ cycloalkyl, C₃ -C₁₈ -alkyl, -alkanoylor -alkenyl interrupted by oxygen, sulfur or by >NR₁₆, C₆ -C₉cycloalkoxycarbonyl, benzoyl, or C₁ -C₈ alkyl-substituted benzoyl, or

R₁, when m=2 and G is a direct bond, is --CO--R₁₇ --CO--, or

R₁, when m=1 and G is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈alkoxy, C₃ -C₁₈ alkoxy interrupted by oxygen, sulfur or by >NR₁₃,benzloxy, C₅ -C₈ cycloalkoxy, unsubstituted or C₁ -C₈ alkyl-substitutedphenoxy, --NR₁₄ R₁₅ or ##STR27## or R₁, when m=2 and G is a group --CR₁₈R₁₉ --CO--, is C₂ -C₁₂ alkanedioxy, or C₃ -C₂₅ alkanedioxy interruptedby oxygen,

R₂ and R₄ are hydrogen,

R₃ and R₅ are each, independently of the other, hydrogen, C₁ -C₁₈ alkyl,C₇ -C₉ phenylalkyl, benzyl, phenyl, C₅ -C₈ cycloalkyl, C₁ -C₈ alkoxy,hydroxy, C₁ -C₁₈ alkanoyloxy, C₃ -C₁₈ alkenoyloxy or benzoyloxy, or aradical of the formula --(CH₂)_(n) --CO--OR₆ or --(CH₂)_(n)--CO--N(R₇)₂, and

R₃, when m=1, is in addition a radical of the formula --Y--E,

R₁₇ is a direct bond, C₁ -C₁₂ alkylene, C₂ -C₁₂ alkylene interrupted byoxygen, sulfur or by >NR₁₆, C₂ -C₁₂ alkenylene, C₂ -C₁₂ alkylidene, C₇-C₁₂ phenylalkylidene, C₅ -C₈ cycloalkylene or phenylene.

Of those there are preferred compounds of formula I, wherein m=1 and

R₁, when G is a direct bond, is hydrogen, C₁ -C₁₈ alkyl, C₂ -C₁₈alkanoyl, C₃ -C₄ alkenyl, C₃ -C₁₈ alkenoyl, benzyl, C₅ -C₈ cycloalkyl,or C₃ -C₁₈ -alkyl or -alkanoyl interrupted by oxygen, or

R₁, when G is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈ alkoxy, C₃-C₁₈ alkoxy interrupted by oxygen, unsubstituted or C₁ -C₈alkyl-substituted phenoxy, --NR₁₄ R₁₅ or ##STR28## R₂, R₄, R₂₁ and R₂₄are each, independently of the other, hydrogen or C₁ -C₄ alkyl,

R₅ is hydrogen or C₁ -C₁₄ alkyl, and

R₃ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₈ alkoxy, --(CH₂)_(n) --CO--OR₆,--(CH₂)_(n) --CO--N(R₇)₂, --(CH₂)_(n) --CO--OR₁₁ or --Y--E.

Among those preference is given to those compounds of formula I wherein

R₁, when G is a direct bond, is hydrogen, C₁ -C₁₈ alkyl, benzyl, allyl,isoallyl, C₁ -C₁₈ alkanoyl, or C₁ -C₁₂ alkanoyl interrupted by oxygen,or

R₁, when G is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈ alkoxy,unsubstituted or C₁ -C₄ alkyl-substituted phenoxy, --NR₁₄ R₁₅ or##STR29## R₂ and R₄ are hydrogen, R₃ and R₅ are each, independently ofthe other, C₁ -C₁₈ alkyl interrupted by oxygen, or C₁ -C₄ alkoxy orcyclohexyl and

R₃ in addition is a group --(CH₂)_(n) --CO--OR₁₁ wherein

R₁₁ is hydrogen or C₁ -C₄ alkyl, and

R₁₄ and R₁₅ are hydrogen or C₁ -C₄ alkyl.

The polyethers comprising at least two, generally from two to eight,preferably two or three, hydroxy groups that are suitable as componentA) are of the type known per se and are prepared, for example, bypolymerisation of epoxides, such as ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, withthemselves, for example in the presence of BF₃, or by addition of thoseepoxides, optionally as a mixture or one after another, to startingcomponents having reactive hydrogen atoms, such as water, alcohols,ammonia or amines, for example ethylene glycol, propylene glycol-(1,3)and -(1,2), trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline,ethanolamine or ethylenediamine. Sucrose polyethers are also suitableaccording to the invention. In many cases, preference is given topolyethers having predominantly (up to 90% by weight, based on all theOH groups present in the polyether) primary OH groups. Also suitable arepolyethers modified by vinyl polymers, such as those formed, forexample, by polymerisation of styrene and acrylonitrile in the presenceof polyethers, and polybutadienes comprising OH groups.

Those compounds generally have molecular weights of from 400-10,000.They are polyhydroxy compounds, especially compounds having from two toeight hydroxy groups, particularly those having a molecular weight offrom 800 to 10,000, preferably from 1000 to 6000, for example polyethershaving at least two, generally from 2 to 8, but preferably from 2 to 4,hydroxy groups, as known per se for the preparation of homogeneous andof cellular polyurethanes.

It is, of course, possible to use mixtures of the above-mentionedcompounds comprising at least two hydrogen atoms that are reactivetowards isocyanates, especially those having a molecular weight of from400 to 10,000.

The compositions according to the invention are used especially in thepreparation of polyurethane, especially in the preparation of softpolyurethane foams. The compositions according to the invention and theproducts prepared from them are effectively protected againstdegradation. In particular core scorching is avoided during foampreparation. In this connection the invention relates also to the use ofthe combination of component B) with component C) and/or component D)for the stabilisation of polyether polyols and/or soft polyurethanefoams prepared therefrom, and also to a process for the preparation ofpolyurethanes which comprises reacting with a polyisocyanate a polyetherpolyol stabilised by the addition of component B) in combination withcomponent C) and/or D), and to the polyurethane and the softpolyurethane foam obtained by that process.

Polyisocyanates that can be used in that process are aliphatic,cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates,for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate andany desired mixtures of those isomers,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and2,6-hexahydrotolylene diisocyanate and any desired mixtures of thoseisomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate,perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate, 1,3- and1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and anydesired mixtures of those isomers, diphenylmethane-2,4'- and/or-4,4'-diisocyanate, naphthylene-1,5-diisocyanate,triphenylmethane-4,4',4"-triisocyanate, polyphenyl-polymethylenepolyisocyanates, such as those obtained by means of aniline-formaldehydecondensation and subsequent phosgenation, m- andp-isocyanatophenylsulfonyl isocyanates, perchlorinatedarylpolyisocyanates, polyisocyanates comprising carbodiimide groups,polyisocyanates comprising allophanate groups, polyisocyanatescomprising isocyanurate groups, polyisocyanates comprising urethanegroups, polyisocyanates comprising acylated urea groups, polyisocyanatescomprising biuret groups, polyisocyanates comprising ester groups,reaction products of the above-mentioned isocyanates with acetals, andpolyisocyanates comprising polymeric fatty acid radicals.

it is also possible to use the distillation residues comprisingisocyanate groups that are obtained in the course of the industrialproduction of isocyanates, optionally dissolved in one or more of theabove-mentioned polyisocyanates. It is also possible to use any desiredmixtures of the above-mentioned polyisocyanates.

Special preference is generally given to polyisocyanates that arereadily available commercially, for example 2,4- and 2,6-tolylenediosocyanate and any desired mixtures of those isomers ("TDI"),polyphenyl-polymethylene polyisocyanates, such as are prepared byaniline-formaldehyde condensation and subsequent phosgenation ("crudeMDI"), and polyisocyanates comprising carbodiimide groups, urethanegroups, allophanate groups, isocyanurate groups, urea groups or biuretgroups ("modified polyisocyanates").

The benzofuran-2-ones of formula Ia and processes for their preparationare described in U.S. Pat. Nos. 4,325,863 and 4,338,244.

The compounds of formula (I) can be prepared in a manner known per se.

For example, and this is preferred, a phenol of formula (V) ##STR30## isreacted with a mandelic acid substituted at the phenyl ring of formula(VI) or (VII) at elevated temperature, especially at temperatures offrom 130° to 200° C. in the melt or in a solvent, optionally under alight vacuum. The reaction is preferably carried out in a solvent, suchas, for example, acetic acid or formic acid, in a temperature range offrom 50° to 130° C. The reaction can be catalysed by adding an acid,such as hydrochloric acid, sulfuric acid or methanesulfonic acid. Thereaction can be carried out, for example, as described in the literaturesources indicated in the introduction of the description.

The 4-hydroxymandelic acids substituted at the phenyl ring of formula(VI) are known in the literature, or can be prepared analogously to themethod, for example, according to W. Bradley et al, J. Chem. Soc. 1956,1622; EP-A-146269 or DE 2 944 295.

The 4-carboxymethoxymandelic acids substituted at the phenyl ring offormula (VII), wherein R₁ is hydroxy, can be etherified according togenerally known etherification conditions starting from phenols offormula (VI), e.g. according to Organikum 1986, pages 194-200, forexample by alkylation under basic conditions with an α-chloroacetic acidderivative of formula ##STR31##

The phenols of formula (V) are also known or can be obtained accordingto processes known per se. ##STR32## Bisphenol compounds of formula VIIIcan be prepared according to Houben-Weyl, Methoden der organischenChemie, Volume 6/1c, 1030.

The 3-(carboxymethoxyphenyl)benzofuran-2-ones of formula I wherein R₁ ishydroxy, m is 1 and G is a group --CR₁₈ R₁₉ --CO-- obtained by thatreaction can be derivatised according to generally known esterificationand amidation methods, e.g. according to Organikum 1986, pages 402-410with m-valent alcohols or with primary or secondary amines of formula##STR33##

The phenols of formula (I) wherein R₁ is hydrogen, G is a direct bondand m=1 obtained by that reaction can be etherified according togenerally known etherification methods, e.g. according to Organikum1986, pages 194-200, for example by alkylation under basic conditionswith an alkyl halide of formula R₁ ¹ Br, a dialkyl sulfate of formula(R₁ ¹)₂ SO₄ or an alkyl tosylate of formula ##STR34## wherein R₁ ¹ hasthe same meaning as R₁ with the exception of hydrogen.

The phenols of formula (I) obtained by that reaction wherein R₁ ishydrogen and G is a direct bond can be esterified according to generallyknown esterifications methods, e.g. according to Organikum 1986, pages402-408, for example by acylation with an acid chloride or acidanhydride of formula R₁ ¹ Cl or R₁ ¹ --O--R₁ ¹ respectively wherein R₁ ¹has the same meaning as R₁ with the exception of hydrogen.

The phenolic and amino anti-oxidants are either commercially availableor can be prepared according to processes known per se.

In the polyol compositions according to the invention, the componentsB), C) and D) together are advantageously present in an amount of from0.01 to 10, for example from 0.05 to 5, preferably from 0.05 to 3, butespecially from 0.1 to 2% by weight. The ratios by weight of B:C, B:Dand B:C:D can vary within wide limits and are advantageously from 10:1to 1:10 or within the limits 10:1:1, 1:1:10 and 1:10:1, e.g. 5:1:1(1:5:1, 1:1:5) or 2:1:1 (1:2:1, 1:1:2) respectively. It may also beadvantageous to use the three components in approximately equimolaramounts.

The polyol compositions according to the invention are preferably usedfor the preparation of polyurethanes, especially polyurethane foams,with propellant advantageously being used.

In the preparation of polyurethanes it is therefore possible in additionto add as propellant water and/or readily volatile organic substances.Suitable organic propellants are, e.g., acetone, ethyl acetate,halo-substituted alkanes, such as methylene chloride, chloroform,ethylidene chloride, vinylidene chloride, monofluorotrichloromethane,chlorodifluoromethane, dichlorodifluoromethane, and also butane, hexane,heptane or diethyl ether. A propellant action can also be achieved byadding compounds that decompose at temperatures above room temperatureto split off gases, for example nitrogen, e.g. azo compounds such asazoisobutyronitrile.

The process according to the invention for the preparation ofpolyurethanes is advantageously carried out in the presence of suitablecatalysts. The catalysts used are catalysts that are known per se, suchas e.g. tertiary amines, such as triethylamine, tributylamine,N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine,N,N,N',N'-tetramethylethylenediamine, 1,4-diazabicyclo-(2,2,2)-octane,N-methyl-N'-dimethylaminoethylpiperazine, N,N-dimethylbenzylamine,bis(N,N-diethylaminoethyl) adipate, N,N-diethylbenzylamine,pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine,N,N,N',N'-tetramethyl-1,3-butanediamine,N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole and2-methylimidazole, also Mannich bases known per se formed from secondaryamines, such as dimethylamine, and aldehydes, preferably formaldehyde,or ketones, such as acetone, methyl ethyl ketone or cyclohexanone, andphenols, such as phenol, nonylphenol or bisphenol.

Examples of tertiary amines comprising hydrogen atoms active towardsisocyanate groups that may be used as catalysts are triethanolamine,triisopropanolamine, N-methyldiethanolamine, N-ethyl-diethanolamine,N,N-dimethyl-ethanolamine, and reaction products thereof with alkyleneoxides, such as propylene oxide and/or ethylene oxide.

Further suitable catalysts are silaamines having carbon-silicon bonds,such as 2,2,4-trimethyl-2-silamorpholine and1,3-diethylaminomethyl-tetramethyl-disiloxane, and nitrogen-containingbases, such as tetraalkylammonium hydroxides, and alkali metalhydroxides, such as sodium hydroxide, alkali metal phenolates, such assodium phenolate, or alkali metal alcoholates, such as sodium methoxide,or hexahydrotriazines, and organometallic compounds, especiallyorganotin compounds, for example tin(II) salts of carboxylic acid, suchas tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate and tin(II)laurate, and the tin(IV) compounds, for example dibutyltin oxide,dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate,dibutyltin maleate or dioctyltin diacetate. It is, of course, possiblefor all of the above-mentioned catalysts to be used in the form ofmixtures.

Other additives known per se, for example surface-active additives, suchas emulsifiers and foam stabilisers, are optionally also present.

Examples of suitable emulsifiers are the sodium salts of ricinoleicsulfonates or salts of fatty acids with amines, such as diethylamineoleate or diethanolamine stearate. Alkali metal or ammonium salts ofsulfonic acids, for example of dodecylbenzenesulfonic acid ordinaphthylmethanedisulfonic acid, or of fatty acids, such as ricinoleicacid, or of polymeric fatty acids, may also be used as surface-activeadditives.

Suitable foam stabilisers are especially polyether siloxanes, especiallywater-soluble representatives thereof. The structure of those compoundsis generally such that a copolymer of ethylene oxide and propylene oxideis bonded to a polydimethylsiloxane radical.

Further additives that may also be present in the compositions arereaction retardants, for example substances with an acid reaction, suchas hydrochloric acid or organic acid halides, also cell regulators ofthe type known per se, such as paraffins or fatty alcohols, ordimethylpolysiloxanes and pigments or dyes and flame-retardants of thetype known per se, for example trischloroethyl phosphate, tricresylphosphate or ammonium phosphate and polyphosphate, and stabilisers thatcounteract the effects of ageing and weathering, plasticisers andfungistats and bacteriostats, as well as fillers, such as bariumsulfate, diatomaceous earth, carbon black or prepared chalk.

Further examples of surface-active additives and foam stabilisers aswell as cell regulators, reaction retardants, stabilisers,flame-retardants, plasticisers, dyes and fillers and also fungistats andbacteriostats that are optionally present and details of the method ofuse and mode of action of those additives are well known to a personskilled in the art.

Using the process according to the invention, it is possible to preparepolyurethane substances in any desired form, such as articles of anydesired form and also fibres. Preference is given, however, to thepreparation of foams, it being possible, by suitable selection of thecomponents, to obtain either flexible or rigid foams or any productsbetween those extremes.

Polyurethane foams are preferably prepared from liquid startingcomponents, with either the starting materials to be reacted with oneanother being mixed together in a one-shot process, or a preadductcontaining NCO groups that is formed from a polyol and an excess ofpolyisocyanate being prepared first and then foamed, for example byreaction with water.

According to the invention, the reaction components are reacted inaccordance with the one-shot process known per se, the prepolymerprocess or the semi-prepolymer process, mechanical devices that are wellknown to a person skilled in the art often being used.

In the preparation of foams, the foaming is often carried out in moulds.In that case, the reaction mixture is introduced into a mould. Suitablemould materials are metals, for example aluminium, or plastics, forexample epoxy resin. In the mould the foamable reaction mixture foams upand forms the moulded article. The formation of foam using a mould canbe carried out in such a manner that the moulding has a cellular surfacestructure, or alternatively, it can be carried out in such a manner thatthe moulding has a dense skin and a cellular core. In this connection,it is possible to introduce into the mould an amount of foamablereaction mixture sufficient for the foam that forms to fill the mouldexactly. It is, however, also possible to introduce more foamablereaction mixture into the mould than is required to fill the interior ofthe mould with foam. In the last-mentioned case, therefore, theoperation is carried out with "overcharging".

In the case of foam formation in a mould "external release agents" knownper se, such as silicone oils, are often used concomitantly. It is,however, also possible to use so-called "internal release agents",optionally in admixture with external release agents.

It is also possible according to the invention to use cold-hardeningfoams. The foams can, of course, alternatively be prepared by means ofblock foaming or by means of the double conveyor belt process which isknown per se.

The process according to the invention can be used to prepare flexible,semi-flexible or hard polyurethane foams. The foams have the uses knownper se for such products, for example as mattresses and upholstery inthe furniture and automobile industries, and also for the manufacture offittings, such as are used in the automobile industry, and finally assound-insulating compositions and as compositions for heat-insulationand low-temperature insulation, for example in the construction sectoror in the refrigeration industry, or in the textile industry, forexample as shoulder pads.

The following Examples further illustrate the invention but withoutimplying any limitation. Unless indicated otherwise, parts andpercentages relate, as in the remainder of the description, to weight.

The components contained in the stabiliser mixtures used are listed inthe following together with their abbreviations:

Benzofuranone components: ##STR35##

Amino anti-oxidants:

A1: Commercial mixture, obtained by reaction of diphenylamine withdiisobutylene, comprising

a) 3% diphenylamine;

b) 14% 4-tert-butyldiphenylamine;

c) 30% compounds from the group

i) 4-tert-octyldiphenylamine,

ii) 4,4'-di-tert-butyldiphenylamine,

iii) 2,4,4'-tris-tert-butyldiphenylamine,

d) 29% compounds from the group

i) 4-tert-butyl-4'-tert-octyldiphenylamine,

ii) o,o'-, m,m'-, or p,p'-di-tert-octyldiphenylamine,

iii) 2,4-di-tert-butyl-4'-tert-octyldiphenylamine,

e) 24% compounds from the group

i) 4,4'-di-tert-octyldiphenylamine (18%),

ii) 2,4-di-tert-octyl-4'-tert-butyldiphenylamine (6%),

A2: ##STR36##

Phenolic anti-oxidants: ##STR37##

EXAMPLES 1-14 Soft polyether/polyurethane foams and the stabilisationthereof

Exactly 470 mg (0.3%, based on the polyol) of a stabiliser mixtureaccording to the invention (see numbered Examples, Tables 1, 2 and 4)are dissolved in 157 g of an antioxidant-free polyether polyol,®Lupranol 2045 (trifunctional polyether polyol having primary hydroxygroups; hydroxy number 35 mg KOH/g, water content less than 0.1%, acidnumber less than 0.1 mg KOH/g).

                  TABLE 4                                                         ______________________________________                                                                Conc. in %                                                          Stabiliser                                                                              based on                                              Ex. No.       mixture   polyol                                                ______________________________________                                         0            --        --                                                    21            B3/P2/A1  0.1/0.1/0.1                                           22            B4/P2/A1  0.1/0.1/0.1                                           23            B5/P2/A1  0.1/0.1/0.1                                           ______________________________________                                    

10.24 g of a solution of 1.74 g of ®TECOSTAB [polysilicone produced byGoldschmidt, DE], 0.48 g of diazabicyclooctane [amine catalysts] and 0.8g of water are added thereto and the reaction mixture is stirredintensively at 100 rpm for 60 seconds.

3.2 g of a solution of 0.32 g of tin octoate (catalyst) in 2.9 g of theabove polyol are then added thereto and the reaction mixture is againstirred intensively for 60 sec. at 100 rpm. Immediately, while stirringintensively, 98 g of an isocyanate (®Lupranat T80 produced by BASF;tolylene-2,4- and -2,6-diisocyanate mixture) are added thereto and after6 sec. the reaction mixture is poured into a lined mould and theexothermic temperature is measured during foaming to form a foam block.

The foam blocks are cooled for 24 hours in a climatic chamber at 5° C.and stored. Slices 2 cm thick are sawed from the middle of the blocksand round (cylindrical) test samples are cut therefrom using a boringtool. The samples are aged in a test tube in the presence of air at 190°C. in a preheated alu-block thermostat.

The yellowing of those samples is determined as the Yellowness Index(YI) in accordance with ASTM D-1925.

The resistance of the stabilised polyurethane foam to oxidation isdetermined by measuring the DSC value (differential scanningcalorimetry, temperature-controlled calorimetry). For that purpose, 20mg of the sample are weighed into an aluminum crucible and heated from astarting temperature of 50° C. at a rate of 5° C./min. The beginning ofthe exothermic oxidation is determined calorimetrically by means of atemperature-controlled measurement against an unstabilised referencesubstance. The temperature at which oxidation begins, and thetemperature difference (ΔT) between the temperature measured for therespective stabilised samples and the corresponding temperature of theunstabilised polyol are given. High values denote a high degree ofresistance to oxidation. The results are summarised in Tables 1 and 2below.

                                      TABLE 1                                     __________________________________________________________________________              Concen-                              Oxidation                                tration                              resistance                               in %,                                acc. to                        Ex.                                                                              Stabiliser                                                                           based on                                                                            YI after oven ageing:          DSC method                     No.                                                                              mixture                                                                              polyol                                                                              0   10 20 30 40 60 80 100                                                                              120 (Min.)                                                                          T (°C.)                                                                    ΔT                   __________________________________________________________________________    0  --     --    -0.7                                                                              44 48 55 57 62             171  0                         1  B1/P2  0.2/0.1                                                                             1.1 2.7                                                                              2.9                                                                              4.8                                                                              7.2                                                                              42 53          198 27                         2  B1/P5  0.2/0.1                                                                             0.3 2.1                                                                              2.6                                                                              3.7                                                                              4.6                                                                              7.9                                                                              16 23 33    205 34                         3  B1/P1  0.2/0.1                                                                             1.1 2.3                                                                              2.9                                                                              3.3                                                                              4.1                                                                              5.6                                                                              6.7                                                                              19 28    208 37                         4  B1/A1  0.2/0.1                                                                             1.1 2.2                                                                              2.4                                                                              3.5                                                                              4.2                                                                              6.5                                                                              12 19 26    210 35                         5  B1/P3  0.2/0.1                                                                             0   1.5                                                                              1.8                                                                              2.9                                                                              3.3                                                                              22 26 33 41    200 29                         6  B1/P2/P1                                                                             0.1/0.1/0.1                                                                         -0.5                                                                              0.8                                                                              1.2                                                                              1.9                                                                              2.1                                                                              3.8                                                                              4.2                                                                              9.4                                                                              13    205 34                         7  B1/P2/P5                                                                             0.1/0.1/0.1                                                                         -0.6                                                                              1.0                                                                              1.4                                                                              2.3                                                                              3.1                                                                              5.5                                                                              10 24 31    208 37                         8  B1/P2/A1                                                                             0.1/0.1/0.1                                                                         -0.2                                                                              0.8                                                                              1.3                                                                              2.2                                                                              2.8                                                                              3.6                                                                              5.3                                                                              9.2                                                                              13    211 40                         9  B1/P2/P1/A1                                                                          0.05 each                                                                           -0.5                                                                              0.7                                                                              1.2                                                                              1.7                                                                              2.4                                                                              4.2                                                                              5.7                                                                              11 21    206 35                         __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________            Concen-                             Oxidation                                 tration                             resistance                                in %,                               acc. to                           Ex.                                                                              Stabiliser                                                                         based on                                                                           YI after oven ageing:          DSC method                        No.                                                                              mixture                                                                            polyol                                                                             0   20 30 40 60  80                                                                              100                                                                              120                                                                              140                                                                              160                                                                              T (°C.)                                                                    ΔT                      __________________________________________________________________________     0 --   --   -0.7                                                                              48 55 57 62                175  0                            10 B2/A2                                                                              0.25/0.05                                                                          1.9 2.4                                                                              4.1                                                                              6.5                                                                              11  16                                                                              22 24 31 33 220 45                            11 B2/P2                                                                              0.25/0.05                                                                          -1.6                                                                              2.1                                                                              4.4                                                                              5.9                                                                              11  23                                                                              34 39 46 53 194 19                            12 B2/P1                                                                              0.25/0.05                                                                          -1.8                                                                              1.7                                                                              2.6                                                                              3.7                                                                              5.1 10                                                                              20 24 36 39 208 33                            13 B2/A1                                                                              0.25/0.05                                                                          -1.7                                                                              1.8                                                                              3.1                                                                              5.9                                                                              7.3 12                                                                              21 27 35 38 208 33                            14 B2/P5                                                                              0.25/0.05                                                                          -1.7                                                                              1.9                                                                              3.5                                                                              4.7                                                                              7.5 13                                                                              23 31 39 43 202 27                            __________________________________________________________________________

The action of the stabiliser combinations according to the invention isexcellent. The yellowing remains low for a long time (low YellownessIndex values denote a low degree of yellowing)

EXAMPLES 15-20

With the DSC method described above, the resistance to oxidation of thepolyether polyols themselves is also measured. The oxidation timeindicated in each case is the time that has passed until the exothermicreaction commences, that is to say long times denote good stabilisation.

The results are illustrated in the following Table 3.

                  TABLE 3                                                         ______________________________________                                        Example              Concentration                                                                             Oxidation                                    No.      Component   [ppm]       time [min]                                   ______________________________________                                        00       --          --           0                                           15       B1          2000        315                                                   P1          1000                                                     16       B1          1000        346                                                   P1          1000                                                              P2          1000                                                     17       B1          2000        272                                                   P5          1000                                                     18       B1          2000        179                                                   A1          1000                                                     19       B1          1000        236                                                   A1          1000                                                              P2          1000                                                     20       B1           500        300                                                   P2           500                                                              P1           500                                                              A1           500                                                     ______________________________________                                    

The compositions according to the invention are shown to have a highdegree of stability.

What is claimed is:
 1. A composition comprisingA) a polyether polyol ormixtures of such polyols, B) at least one benzofuranone derivative offormula I ##STR38## wherein L is oxygen or, when G is a direct bond andR₁ is hydrogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy, does not exist,G is adirect bond or a group --CR₁₈ R₁₉ --CO--, m is 1 or 2, R₁, when m=1 andG is a direct bond, is hydrogen, C₁ -C₂₅ alkyl, C₃ -C₂₅ alkenyl, C₂ -C₁₈alkanoyl, C₃ -C₂₅ alkenoyl, C₇ -C₉ phenylalkyl, unsubstituted or C₁ -C₄alkyl-substituted phenyl, unsubstituted or C₁ -C₄ alkyl-substituted C₅-C₈ cycloalkyl, C₃ -C₂₅ -alkyl, -alkanoyl or -alkenyl interrupted byoxygen, sulfur or by >NR₁₆, C₆ -C₉ cycloalkoxycarbonyl, benzoyl or C₁-C₁₂ alkyl-substituted benzoyl, or R₁, when m=2 and G is a direct bond,is --CO--R₁₇ --CO--, or R₁, when m=1 and G is a group --CR₁₈ R₁₉ --CO--,is hydroxy, C₁ -C₃₀ alkoxy, C₃ -C₃₀ alkoxy interrupted by oxygen, sulfuror by >NR₁₃, C₇ -C₉ phenylalkoxy, C₅ -C₁₂ cycloalkoxy, C₂ -C₁₈alkenyloxy, unsubstituted or C₁ -C₁₂ alkyl-substituted phenoxy,##STR39## or R₁, when m=2 and G is a group --CR₁₈ R₁₉ --CO--, is C₂ -C₁₂alkanedioxy, C₃ -C₂₅ alkanedioxy interrupted by oxygen, sulfur or by>NR₁₆, ##STR40## R₂ and R₄ are each, independently of the other,hydrogen or C₁ -C₆ alkyl, R₃ and R₅ are each, independently of theother, hydrogen, C₁ -C₂₅ alkyl, C₇ -C₉ phenylalkyl, unsubstituted or C₁-C₄ alkyl-substituted phenyl, unsubstituted or C₁ -C₄ alkyl-substitutedC₅ -C₈ cycloalkyl, C₁ -C₁₈ alkoxy, hydroxy, C₁ -C₂₅ alkanoyloxy, C₃ -C₂₅alkenoyloxy, C₃ -C₂₅ alkenyloxy interrupted by oxygen, sulfur or by>NR₁₆, C₆ -C₉ cycloalkylcarbonyloxy, benzoyloxy or C₁ -C₁₂alkyl-substituted benzoyloxy, or a radical of the formula --(CH₂)_(n)--CO--OR₆, --(CH₂)_(n) --COR₁₁ or --(CH₂)_(n) --CO--N(R₇)₂,R₃, when m=1,is furthermore a radical of the formula ##STR41## when m=1 and R₄, R₅,R₂₁ R₂₄ are hydrogen, R₃ in addition is a radical of the formula##STR42## R₂ together with R₃ or R₄ together with R₅, in each casetogether with the carbon atoms to which they are bonded, form a phenylring, R₆ is hydrogen, C₂ -C₁₈ alkyl, C₁ -C₁₈ alkyl interrupted by oxygenor by sulfur, C₃ -C₁₆ dialkylaminoalkyl, cyclohexyl, phenyl, or phenylsubstituted by from 1 to 3 alkyl radicals together having a maximum of18 carbon atoms, n is 0, 1 or 2, the substituents R₇ are each,independently of the other, hydrogen, C₁ -C₁₈ alkyl, cyclopentyl,cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals togetherhaving a maximum of 16 carbon atoms, a radical of the formula --C₂ H₄OH, --C₂ H₄ --O--C_(q) H_(2q+1) or --C₂ H₄ --O--CO--R₁₀, together withthe nitrogen atom to which they are bonded, form a piperidine ormorpholine radical, wherein q is 1 to 18, R₈ is hydrogen, alkyl havingfrom 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl,phenyl substituted by 1 or 2 alkyl radicals together having a maximum of16 carbon atoms, or benzyl, R₉ is alkyl having from 1 to 18 carbonatoms, R₁₀ is hydrogen, alkyl having from 1 to 22 carbon atoms orcycloalkyl having from 5 to 12 carbon atoms R₁₁ is hydroxy, ##EQU2## C₁-C₁₈ alkoxy or --NR₁₄ R₁₅, R₁₂ and R₁₃ are each, independently of theother, hydrogen, C₁ -C₁₂ alkyl or phenyl, or form together with theC-atom to which they are bound a C₅ -C₇ -alkylidene-ring which isunsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl groups, R₁₄ and R₁₅are each, independently of the other, hydrogen or C₁ -C₁₈ alkyl, M is anr-valent metal cation and r is 1, 2 or 3, A* is an alkylene radicalhaving from 2 to 22 carbon atoms that may or may not be interrupted bynitrogen, oxygen or by sulfur, Y is --O--, --S--, --SO--, --SO₂ -- or--C(R₂₀)₂ --, wherein the substituents R₂₀ are each, independently ofthe other, hydrogen, C₁ -C₁₆ alkyl, phenyl or a radical of the formula--(CH₂)_(n) --CO--OR₆ or --(CH₂)_(n) --CO--N(R₇)₂, E is a radical of theformula ##STR43## R₁₆ is hydrogen or C₁ -C₈ alkyl, R₁₇ is a direct bond,C₁ -C₁₈ alkylene, C₂ -C₁₈ alkylene interrupted by oxygen, sulfur or by>NR₁₆, C₂ -C₁₈ alkenylene, C₂ -C₂₀ alkylidene, C₇ -C₂₀ phenylalkylidene,C₅ -C₈ cycloalkylene, C₇ -C₈ bicycloalkylene or phenylene, R₁₈ and R₁₉are each, independently of the other, hydrogen, C₁ -C₄ alkyl or phenyl,and R₂₁, R₂₂, R₂₃ R₂₄ are each, independently of the others, hydrogen,C₁ -C₄ alkyl or C₁ -C₄ alkoxy, provided that at least one of theradicals R₂₁, R₂₂, R₂₃ and R₂₄ is hydrogen, C) at least one compoundfrom the group of the phenolic anti-oxidants, and D) at least onecompound of formula III ##STR44## wherein R₃₈ is C₁ -C₁₈ alkyl,phenyl-C₁ -C₄ alkyl, C₅ -C₁₂ cycloalkyl, phenyl, naphthyl, or phenyl ornaphthyl substituted by C₁ -C₁₂ alkyl or by C₁ -C₁₂ alkoxy,R₃₉ isphenyl, naphthyl, or phenyl or naphthyl substituted by C₁ -C₁₂ alkyl orby C₁ -C₁₂ alkoxy, or R₃₈ and R₃₉ together form a radical of the formulaIV ##STR45## wherein R₄₀ and R₄₁ are hydrogen or C₁ -C₁₈ alkyl or R₄₁ ishydrogen or C₁ -C₁₈ alkyl and R₄₀ together with R₄₂ forms a group of theformula ##STR46## or, a composition comprising (A), (B) and (D).
 2. Acomposition according to claim 1, comprisingB) at least onebenzofuranone derivative of formula Ia ##STR47## wherein R.sup.•₁ isphenyl, or phenyl substituted by from 1 to 3 alkyl radicals togetherhaving a maximum of 12 carbon atoms or by alkoxy having from 1 to 12carbon atoms,R.sup.•₂ is hydrogen and R.sup.•₄ is hydrogen, alkyl havingfrom 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine, R.sup.•₃has the same meaning as R.sup.•₂ or R.sup.•₄ or is a radical of theformula --(CH₂)_(n) --CO--OR.sup.•₆, --(CH₂)_(n) --CO--N(R.sup.•₇)₂,--(CH₂)_(n) --CO--O--A.sup.• --O--CO--(CH₂)_(n) --E.sup.•, --(CH₂)_(n)--CO--NR.sup.•₈ --A.sup.• --NR.sup.•₈ --CO--(CH₂)_(n) --E.sup.•,--(CH₂)_(n) --CO--NR.sup.•₈ --A.sup.• --O--CO--(CH₂)_(n) --E.sup.•,##STR48## --CH₂ --S--R.sup.•₉, --CH(C₆ H₅)--CO--R.sup.•₆ or --Y.sup.•--E.sup.• wherein R.sup.•₆ is hydrogen, alkyl having from 2 to 18 carbonatoms, alkyl having from 1 to 18 carbon atoms that is interrupted byoxygen or by sulfur, dialkylaminoalkyl having a total of from 3 to 16carbon atoms, cyclopentyl, cyclohexyl, phenyl, or phenyl substituted byfrom 1 to 3 alkyl radicals together having a maximum of 18 carbon atoms,n is 0, 1 or 2, the substituents R.sup.•₇ are each, independently of theother, hydrogen, alkyl having from 1 to 18 carbon atoms, cyclopentyl,cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals togetherhaving a maximum of 16 carbon atoms, a radical of the formula --C₂ H₄OH, --C₂ H₄ --O--C_(q) H_(2q+1) or --C₂ H₄ --O--CO--R.sup.•₁₀, or,together with the nitrogen atom to which they are bonded, form apiperidine or morpholine radical, q is from 1 to 18, R.sup.•₁₀ ishydrogen, alkyl having from 1 to 22 carbon atoms or cycloalkyl havingfrom 5 to 12 carbon atoms, A.sup.• is an alkylene radical having from 2to 22 carbon atoms that may or may not be interupted by nitrogen, oxygenor by sulfur, R.sup.•₈ is hydrogen, alkyl having from 1 to 18 carbonatoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2alkyl radicals together having a maximum of 16 carbon atoms, or benzyl,R.sup.•₉ is alkyl having from 1 to 18 carbon atoms, Y.sup.• is --O--,--S--, --SO--, --SO₂ -- or --C(R.sup.•₁₁)₂ --, the substituentsR.sup.•₁₁, are each, independently of the other, hydrogen, alkyl whereinthe alkyl radicals together have a maximum of 16 carbon atoms, phenyl ora radical of the formula --(CH₂)_(n) --CO--OR.sup.•₆ or --(CH₂)_(n)--CO--N(R.sup.•₇)₂ wherein n, R.sup.•₆ and R.sup.•₇ have the meaningsgiven, E.sup.• is a radical of the formula ##STR49## wherein R.sup.•₁,R.sup.•₂ and R.sup.•₄ have the meanings given, and R.sup.•₅ is hydrogen,alkyl having from 1 to 20 carbon atoms, cyclopentyl, cyclohexyl,chlorine or a radical of the formula --(CH₂)_(n) --CO--OR.sup.•₆ or--(CH₂)_(n) --CO--N(R.sup.•₇)₂ wherein R₆.sup.• and R₇.sup.• have themeanings given, or R₅.sup.• together with R₄.sup.• forms atetramethylene radical.
 3. A composition according to claim 1, whereincomponent C) corresponds to formula II ##STR50## wherein A is hydrogen,C₁ -C₂₄ alkyl, C₅ -C₁₂ cycloalkyl, phenyl-C₁ -C₄ alkyl, phenyl or agroup --CH₂ --S--R₂₅ or ##STR51## D is C₁ -C₂₄ alkyl, C₅ -C₁₂cycloalkyl, phenyl-C₁ -C₄ alkyl, phenyl or a group --CH₂ --S--R₂₅,X ishydrogen, C₁ -C₁₈ alkyl or one of the groups --C_(a) H_(2a) --S_(q)--R₂₆, --C_(b) H_(2b) --CO--OR₂₇, --C_(b) H_(2b) --CO--N(R₂₉)(R₃₀),--CH₂ N(R₃₄)(R₃₅), ##STR52## R is hydrogen or a group of the formula--CO--CH═CH₂, G* is hydrogen or C₁ -C₁₂ alkyl, R₂₅ is C₁ -C₁₈ alkyl,phenyl or a group --(CH₂)_(c) --CO--OR₂₈ or --CH₂ CH₂ OR₃₃, R₂₆ ishydrogen, C₁ -C₁₈ alkyl, phenyl, benzyl or a group ##STR53## R₂₇ is C₁-C₃₀ alkyl or one of the groups --CHR₃₁ --CH₂ --S--R₃₂, ##STR54##wherein Q is C₂ -C₈ alkylene, C₄ -C₆ thiaalkylene or a group --CH₂ CH₂(OCH₂ CH₂)_(d) --, R₂₈ is C₁ -C₂₄ alkyl, R₂₉ is hydrogen, C₁ -C₁₈ alkylor cyclohexyl, R₃₀ is C₁ -C₁₈ alkyl, cyclohexyl, phenyl, phenylsubstituted by C₁ -C₁₈ alkyl, or one of the groups ##STR55## R₂₉ and R₃₀together are C₄ -C₈ alkylene that may be interrupted by --O-- or --NH--,R₃₁ is hydrogen, C₁ -C₄ alkyl or phenyl, R₃₂ is C₁ -C₁₈ alkyl, R₃₃ ishydrogen, C₁ -C₂₄ alkyl, phenyl, C₂ -C₁₈ alkanoyl or benzoyl, R₃₄ is C₁-C₁₈ alkyl, cyclohexyl, phenyl, phenyl substituted by C₁ -C₁₈ alkyl, ora group ##STR56## R₃₅ is hydrogen, C₁ -C₁₈ alkyl, cyclohexyl, or a group##STR57## R₃₄ and R₃₅ together are C₄ -C₈ alkylene, which may beinterrupted by --O-- or --NH--, R₃₆ and R₃₇ are --S--C₁ -C₁₈ alkyl, a is0, 1, 2 or 3, b is 0, 1, 2 or 3, c is 1 or 2, d is from 1 to 5, f isfrom 2 to 8 and q is 1, 2, 3 or
 4. 4. A composition according to claim3, whereinA is hydrogen, C₁ -C₈ alkyl, cyclohexyl, phenyl or a group--CH₂ --R₃₆ or ##STR58## D is C₁ -C₈ alkyl, cyclohexyl, phenyl or agroup --CH₂ --R₃₇, X is hydrogen, C₁ -C₈ alkyl or one of the groups--C_(a) H_(2a) --S_(q) --R₂₆, --C_(b) H_(2b) --CO--OR₂₇, --CH₂N(R₃₄)(R₃₅), ##STR59## R₂₆ is C₁ -C₁₂ alkyl, phenyl or a group--(CH₂)_(c) --CO--OR₂₈, R₂₇ is C₁ -C₁₈ alkyl or a group ##STR60##wherein Q is C₂ -C₈ alkylene, --CH₂ --CH₂ --S--CH₂ CH₂ or a group --CH₂CH₂ (OCH₂ CH₂)_(d) --, R₂₈ is C₁ -C₁₈ alkyl, R₃₄ and R₃₅ are each,independently of the other, hydrogen or C₁ -C₁₂ alkyl or R₃₄ and R₃₅together are C₄ -C₈ alkylene which may be interrupted by --O-- or--NH--, a is 1 or 2, b is 1 or 2, c is 1 or 2, and d is 1, 2 or
 3. 5. Acomposition according to claim 4, whereinA is hydrogen, C₁ -C₆ alkyl,--CH₂ --R₃₆ or a group ##STR61## D is hydrogen or C₁ -C₁₈ alkyl, and Xis hydrogen, C₁ -C₄ alkyl, --CH₂ --R₃₆ or a group of the formula##STR62##
 6. A composition according to claim 1, wherein R₃₈ and R₃₉ areeach, independently of the other, phenyl or phenyl substituted by C₁-C₁₂ alkyl, or together form a radical of the formula IV.
 7. Acomposition according to claim 1 whereinR₃₈ and R₃₉ form a radical ofthe formula IV wherein R₄₀ and R₄₁ are C₆ -C₁₂ alkyl and R₄₂ ishydrogen,or component D) is a commercial mixture obtained by reactingdiphenylamine with diisobutylene, comprising a) diphenylamine; b)4-tert-butyldiphenylamine; c) compounds from the groupi)4-tert-octyldiphenylamine, ii) 4,4'-di-tert-butyldiphenylamine, iii)2,4,4'-tris-tert-butyldiphenylamine, d) compounds from the groupi)4-tert-butyl-4'-tert-octyldiphenylamine, ii) o,o'-,m,m'-, orp,p'-di-tert-octyldiphenylamine, iii)2,4-di-tert-butyl-4'-tert-octyldiphenylamine, e) compounds from thegroupi) 4,4'-di-tert-octyldiphenylamine, ii)2,4,-di-tert-octyl-4'-tert-butyldiphenylamine, and wherein not more than5% of component a), 8 to 15% b), 24 to 32% c), 23 to 34% d) and 21 to34% e) are present.
 8. A composition according to claim 1, wherein R₂ ishydrogen.
 9. A composition according to claim 1, whereinR₁, when m=1 andG is a direct bond, is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₈ alkenyl, C₂ -C₁₈alkanoyl, C₃ -C₁₈ alkenoyl, benzyl, phenyl or C₁ -C₄ alkyl-substitutedphenyl, C₅ -C₈ cycloalkyl, C₃ -C₁₈ -alkyl, -alkanoyl or -alkenylinterrupted by oxygen, sulfur or by >NR₁₆, C₆ -C₉ cycloalkoxycarbonyl,benzoyl, or C₁ -C₈ alkyl-substituted benzoyl, or R₁, when m=2 and G is adirect bond, is --CO--R₁₇ --CO--, or R₁, when m=1 and G is a group--CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈ alkoxy, C₃ -C₁₈ alkoxyinterrupted by oxygen, sulfur or by >NR₁₃, benzyloxy, C₅ -C₈cycloalkoxy, unsubstituted or C₁ -C₈ alkyl-substituted phenoxy, -NR₁₄R₁₅ or ##STR63## or R₁, when m=2 and G is a group --CR₁₈ R₁₉ --CO--, isC₂ -C₁₂ alkanedioxy, or C₃ -C₂₅ alkanedioxy interrupted by oxygen, R₂and R₄ are hydrogen, R₃ and R₅ are each, independently of the other,hydrogen, C₁ -C₁₈ alkyl, C₇ -C₉ phenylalkyl, benzyl, phenyl, C₅ -C₈cycloalkyl, C₁ -C₈ alkoxy, hydroxy, C₁ -C₁₈ alkanoyloxy, C₃ -C₁₈alkenoyloxy or benzoyloxy, or a radical of the formula --(CH₂)_(n)--CO--OR₆ or --(CH₂)_(n) --CO--N(R₇)₂, and R₃, when m=1, is in additiona radical of the formula --Y--E, R₁₇ is a direct bond, C₁ -C₁₂ alkylene,C₂ -C₁₂ alkylene interrupted by oxygen, sulfur or by >NR₁₆, C₂ -C₁₂alkenylene, C₂ -C₁₂ alkylidene, C₇ -C₁₂ phenylalkylidene, C₅ -C₈cycloalkylene or phenylene.
 10. A composition according to claim 9,wherein m=1 and,R₁, when G is a direct bond, is hydrogen, C₁ -C₁₈ alkyl,C₂ -C₁₈ alkanoyl, C₃ -C₄ alkenyl, C₃ -C₁₈ alkenoyl, benzyl, C₅ -C₈cycloalkyl, or C₃ -C₁₈ alkyl or -alkanoyl interrupted by oxygen, or R₁,when G is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈ alkoxy, C₃ -C₁₈alkoxy interrupted by oxygen, unsubstituted or C₁ -C₈ alkyl-substitutedphenoxy, --NR₁₄ R₁₅ or ##STR64## R₂, R₄, R₂₁ and R₂₄ are each,independently of the other, hydrogen or C₁ -C₄ alkyl, R₅ is hydrogen orC₁ -C₁₄ alkyl, and R₃ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₈ alkoxy,--(CH₂)_(n) --CO--OR₆, --(CH₂)_(n) --CO--N(R₇)₂, --(CH₂)_(n) --CO--OR₁₁or --Y--E.
 11. A composition according to claim 10, wherein,R₁, when Gis a direct bond, is hydrogen, C₁ -C₁₈ alkyl, benzyl, allyl, isoallyl,C₁ -C₁₈ alkanoyl, or C₁ -C₁₂ alkanoyl interrupted by oxygen, or R₁, whenG is a group --CR₁₈ R₁₉ --CO--, is hydroxy, C₁ -C₁₈ alkoxy,unsubstituted or C₁ -C₄ alkyl-substituted phenoxy, --NR₁₄ R₁₅ or##STR65## R₂ and R₄ are hydrogen, R₃ and R₅ are each, independently ofthe other, C₁ -C₁₈ alkyl interrupted by oxygen, or C₁ -C₄ alkoxy orcyclohexyl and R₃ in addition is a group --(CH₂)_(n) --CO--OR₁₁ whereinR₁₁ is hydrogen or C₁ -C₄ alkyl, and R₁₄ and R₁₅ are hydrogen or C₁ -C₄alkyl.
 12. A process for the stabilisation of polyether polyols whichcomprises adding thereto at least one compound of formula I according toclaim 1 in combination with at least one compound from the group of thephenolic anti-oxidants, and/or at least one compound from the group ofthe amino anti-oxidants of the secondary amine type.